CN102918460A

CN102918460A - Photosensitive siloxane composition, cured film formed form same, and element having cured film

Info

Publication number: CN102918460A
Application number: CN2011800282708A
Authority: CN
Inventors: 妹尾将秀; 藤原健典; 福原将; 诹访充史; 山本荣悟; 內田圭一
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2010-06-09
Filing date: 2011-06-02
Publication date: 2013-02-06
Anticipated expiration: 2031-06-02
Also published as: WO2011155382A1; JP5696665B2; TW201211112A; CN102918460B; KR20130090750A; JPWO2011155382A1; TWI482802B; KR101761181B1

Abstract

Disclosed is a photosensitive siloxane composition having: (a) a polysiloxane synthesized by reacting at least one organosilane represented by general formula 1, (b) a quinone diazide compound, (c) a solvent, and (d) the silicate compound represented by general formula 2. (In formula 1, R1 represents any of hydrogen, an alkyl group having 1-10 carbon atoms, an alkenyl group having 2-10 carbon atoms, or an aryl group having 6-15 carbon atoms; the plurality of R1 may be the same or different. R2 represents any of hydrogen, an alkyl group having 1-6 carbon atoms, an acyl group having 2-6 carbon atoms, or an aryl group having 6-15 carbon atoms; the plurality of R2 may be the same or different; and n represents an integer from 0 to 3.) (In formula 2, R3 to R6 each independently represents any of hydrogen, an alkyl group having 1-6 carbon atoms, an acyl group having 2-6 carbon atoms; or an aryl group having 6-15 carbon atoms; and p represents an integer from 2 to 10.) Provided is the photosensitive siloxane composition that can yield a cured film having the properties of high heat resistance and high transparency, and of which the chemical resistance is favorable.

Description

Photosensitive siloxane composition, by its cured film that forms and element with cured film

Technical field

The present invention relates to be used to form thin film transistor (TFT) (TFT) substrate of liquid crystal display cells, organic EL display element etc. with the photosensitive siloxane composition of the core of the interlayer dielectric of the diaphragm of planarization film, touch-screen, dielectric film, semiconductor element or optical waveguide, cladding material etc., by its cured film that forms and element with this cured film.

Background technology

In recent years, for liquid crystal display, OLED display etc., require to realize further fine, high degree of resolution.

In addition, in liquid crystal display etc., the employing of touch-screen comes to life in recent years, and particularly the touch-screen of electrostatic capacitance mode is subject to attracting attention of people.

The prior art document

Patent documentation

For example in patent documentation 1, for liquid crystal display, OLED display etc., as the method that realizes further fine, high degree of resolution, put down in writing the method that improves the aperture opening ratio of display device.The method is by transparent planarization film being arranged on the top of TFT substrate as diaphragm, can making data line and pixel electrode overlapping, compared with prior art having improved the method for aperture opening ratio.

As the material of this TFT substrate with planarization film, the characteristic that need to have high-fire resistance, high transparent, and for TFT electrode of substrate and ITO electrode are connect, need to form the perforation pattern about number μ m～50 μ m, generally can use the positive light sensitivity material.

In the patent documentation 2,3, as the representative materials of positive light sensitivity material, put down in writing the material that in acryl resin, has made up diazonium quinone (キノ Application ジアジ De) compound.

On the other hand, material as the characteristic with high-fire resistance, high transparent, known polysiloxane, put down in writing in the patent documentation 4,5,6 in order to give the photonasty of its eurymeric, and having made up the material of diazonium naphtoquinone compounds, the thermotolerance of these materials is high, even pass through pyroprocessing, the shortcoming that does not also crack etc. can obtain high transparent cured film.

Patent documentation 1: Japanese kokai publication hei 9-152625 communique (claim 1)

Patent documentation 2: TOHKEMY 2001-281853 communique (claim 1)

Patent documentation 3: TOHKEMY 2001-281861 communique (claim 1)

Patent documentation 4: TOHKEMY 2006-178436 communique (claim 1)

Patent documentation 5: TOHKEMY 2009-211033 communique (claim 1)

Patent documentation 6: TOHKEMY 2010-33005 communique (claim 1).

Summary of the invention

But the transparent planarization film of patent documentation 1 is owing to being the film that has used acrylic materials, so thermotolerance is insufficient.

In addition, the thermotolerance of the material of record is insufficient in the patent documentation 2,3, has because the pyroprocessing of substrate causes cured film painted the problem that the transparency reduces.In addition; for touch-screen; in order to improve performance; studied high transparence and high conductionization that utilization is carried out as the high temperature film forming of the ITO of transparency electrode member, accompanied with it, even for the material as diaphragm, dielectric film; also require thermotolerance; but for these acryhic materials, thermotolerance is insufficient, can not form high transparent, the high ITO that conducts electricity.

The material of record is insufficient for the patience of the liquid medicine such as ITO etching solution in the patent documentation 4,5,6, requires the raising of resistance to chemical reagents.

The present invention is the invention of making in view of the above fact, and its problem is to provide the photosensitive siloxane composition of the good cured film of the characteristic that can obtain having high-fire resistance, high transparent and resistance to chemical reagents.In addition, other problem of the present invention be to provide the TFT substrate that formed by above-mentioned photosensitive siloxane composition with planarization film, touch-screen with the cured film of dielectric film etc. with have the element of the liquid crystal display cells etc. of this cured film.

That is, purpose of the present invention make by containing (a) reaction more than a kind of the organosilane shown in the general formula (1) come synthetic polysiloxane, (b) diazonium naphtoquinone compounds, (c) solvent and (d) photosensitive siloxane composition of the silicate ester compound shown in the general formula (2) realize.

[changing 1]

(in the formula, R ¹Expression hydrogen, carbon number are that 1～10 alkyl, carbon number are that 2～10 thiazolinyl, carbon number are any one of 6～15 aryl, a plurality of R ¹Can be identical or different respectively, R ²Expression hydrogen, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any one of 6～15 aryl, a plurality of R ²Can be identical or different respectively, n represents 0～3 integer.）

[changing 2]

(in the formula, R ³～R ⁶Represent independently that respectively hydrogen, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any one of 6～15 aryl.P represents 2～10 integer.）。

According to photosensitive siloxane composition of the present invention, can obtain having the characteristic of high-fire resistance, high transparent, and the good cured film of resistance to chemical reagents.In addition, the cured film of gained can be suitable as the TFT substrate with planarization film or touch-screen dielectric film.

Embodiment

Photosensitive siloxane composition of the present invention is the photosensitive siloxane composition that contains (a) polysiloxane, (b) diazonium naphtoquinone compounds, (c) solvent, (d) silicate ester compound.

Photosensitive siloxane composition of the present invention contains (a) polysiloxane.The polysiloxane that uses among the present invention is to come synthetic polysiloxane by the reaction more than a kind that makes the organosilane shown in the general formula (1).

[changing 3]

(in the formula, R ¹Expression hydrogen, carbon number are that 1～10 alkyl, carbon number are that 2～10 thiazolinyl, carbon number are any one of 6～15 aryl, a plurality of R ¹Can be identical or different respectively.R ²Expression hydrogen, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any one of 6～15 aryl, a plurality of R ²Can be identical or different respectively.N represents 0～3 integer.）。

In the organosilane shown in the general formula (1), R ¹Expression hydrogen, carbon number are that 1～10 alkyl, carbon number are that 2～10 thiazolinyl, carbon number are any one of 6～15 aryl, a plurality of R ¹Can be identical or different respectively.In addition, these alkyl, thiazolinyl, aryl all can be without any of substituted compound, substituted compound, can select according to the characteristic of composition.Concrete example as alkyl, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive decyl, trifluoromethyl, 3,3,3-trifluoro propyl, 3-glycidoxy propyl group, 2-(3,4-epoxycyclohexyl) ethyl, ((3-ethyl-3-oxetanyl) methoxyl) propyl group, 3-aminopropyl, 3-sulfydryl propyl group, 3-isocyanate group propyl group.The concrete example of thiazolinyl can be enumerated vinyl, 3-acryloxy propyl group, 3-methacryloxypropyl.The concrete example of aryl can be enumerated phenyl, tolyl, p-hydroxybenzene, 1-(p-hydroxybenzene) ethyl, 2-(p-hydroxybenzene) ethyl, 4-hydroxyl-5-(p-hydroxybenzene ketonic oxygen base) amyl group, naphthyl.

The R of general formula (1) ²Expression hydrogen, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any one of 6～15 aryl, a plurality of R ²Can be identical or different respectively.In addition, these alkyl, acyl group, aryl all can be any one without substituted compound, substituted compound, can select according to the characteristic of composition.The concrete example of alkyl can be enumerated methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl.The concrete example of acyl group can be enumerated acetyl group.The concrete example of aryl can be enumerated phenyl.

The n of general formula (1) represents 0～3 integer.During n=0, being 4 functional silanes, during n=1, is 3 functional silanes, during n=2, is 2 functional silanes, during x=3, is 1 functional silanes.

Concrete example as the organosilane shown in the general formula (1), can enumerate tetramethoxy-silicane, tetraethoxysilane, the tetrem acyloxy silane, 4 functional silanes of tetraphenoxy-silicane alkane etc., methyltrimethoxy silane, methyl triethoxysilane, methyl three isopropoxy silane, methyl three n-butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, the normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl trimethoxy silane, the n-hexyl triethoxysilane, the decyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy propyl trimethoxy silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, the p-hydroxybenzene trimethoxy silane, the 1-(p-hydroxybenzene) ethyl trimethoxy silane, the 2-(p-hydroxybenzene) ethyl trimethoxy silane, 4-hydroxyl-5-(p-hydroxybenzene ketonic oxygen base) amyltrimethoxysilane, the trifluoromethyl trimethoxy silane, the trifluoromethyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane, the 3-TSL 8330, APTES, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, ((3-ethyl-3-oxetanyl) methoxyl) propyl trimethoxy silicane, ((3-ethyl-3-oxetanyl) methoxyl) propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, 3 functional silanes of 3-trimethoxy-silylpropyl succinic acid etc., dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diacetoxy silane, di-n-butyl dimethoxy silane, dimethoxydiphenylsilane, (3-glycidoxy propyl group) methyl dimethoxysilane, 2 functional silanes of (3-glycidoxy propyl group) methyldiethoxysilane etc., the trimethyl methoxy silane, three normal-butyl Ethoxysilanes, (3-glycidoxy propyl group) dimethyl methyl TMOS, 1 functional silanes of (3-glycidoxy propyl group) dimethylethoxysilane etc.And these organosilanes may be used alone, or two or more kinds may be used in combination.In these organosilanes, consider from the resistance to cracking line of cured film and the angle of hardness, preferably use 3 functional silanes.

In addition, in the polysiloxane that the present invention uses, can use a polysiloxane that reacts and synthesize more than a kind of the organosilane shown in (d) silicate ester compound following by making and the general formula (1).By making the silicate ester compound reaction, the pattern resolution improves.Think that this is that the pattern in the time of can suppressing heat curing is lax because by take in polyfunctional silicate ester compound in polysiloxane, the glass transformation temperature of film uprises.

Mixture ratio when using silicate ester compound is not particularly limited, but preferably take Si atomic molar number with respect to the Si atomic molar number of whole polymkeric substance as below 50%.Silicate ester compound is when this scope, and the compatibility of polysiloxane and diazonium naphtoquinone compounds improves, and can keep the transparency of cured film.And with respect to the Si atomic molar number of whole polymkeric substance, the Si atomic molar of silicate ester compound is than being tried to achieve by the peak that comes from the Si-C key and the integration ratio at the peak that comes from the Si-O key in IR.In the time of can not trying to achieve more than the coincidence at peak, can utilize 1H-NMR, 13C-NMR, IR, TOF-MS etc. to determine the structure of the monomers beyond the silicate ester compounds, and then be tried to achieve by the ratio of the gas that in elemental microanalysis method, produces and residual ash (supposing all to be SiO2).

In addition, in the polysiloxane that the present invention uses, for improving with the compatibility of following (b) diazonium naphtoquinone compounds, not producing and be separated and form the purpose of the cured film of homogeneous, the containing ratio of the phenyl in the polysiloxane is preferably more than 30 % by mole with respect to the Si atom, more preferably more than 40 % by mole.The containing ratio of phenyl when this preferred scope, polysiloxane and diazonium naphtoquinone compounds in coating, dry, heat curing is medium, be difficult to cause be separated, so film can not produce gonorrhoea, can keep the high transparent of cured film.In addition, as the higher limit of the containing ratio of phenyl, be below 70 % by mole with respect to the Si atom preferably.The containing ratio of phenyl when this preferred scope, crosslinked when fully producing heat curing, the resistance to chemical reagents excellence of cured film.The containing ratio of phenyl for example can be by measuring the 29Si-NMR of polysiloxane, by bonding recently the trying to achieve of peak area of peak area and the Si that does not have the bonding phenyl of Si of this phenyl.

In addition, the weight-average molecular weight of the polysiloxane that uses among the present invention (Mw) is not particularly limited, and preferably utilizes the GPC(gel permeation chromatography) measure take the weight-average molecular weight of polystyrene conversion as 1000～100000, more preferably 2000～50000.When Mw was this preferred scope, filming property was good, and the dissolubility in the developer solution when pattern forms is also good.

The polysiloxane that uses among the present invention can synthesize by the monomer hydrolysis and the part condensation that make the organosilane shown in the general formula (1) etc.Hydrolysis and part condensation can be used general method.The catalyzer that for example add solvent, water in potpourri, adds as required adds thermal agitation about 0.5～100 hour at 50～150 ℃.And, in the stirring, can remove by the be hydrolyzed distillation of accessory substance (alcohol of methyl alcohol etc.), condensation by-product (water) of distillation as required.

Above-mentioned reaction dissolvent is not particularly limited, and usually can use with following (c) solvent is same solvent.The addition of solvent is 10～1000 mass parts with respect to monomer 100 mass parts of organosilane etc. preferably.The addition that is used in addition the water of hydrolysis reaction is 0.5～2 mole with respect to 1 mole of hydrolization group preferably.

The catalyzer that adds as required is not particularly limited, and preferably uses acid catalyst, base catalyst.The concrete example of acid catalyst can be enumerated hydrochloric acid, nitric acid, sulfuric acid, fluoric acid, phosphoric acid, acetic acid, trifluoracetic acid, formic acid, polybasic carboxylic acid or its acid anhydrides, ion exchange resin.The concrete example of base catalyst can be enumerated triethylamine, tripropylamine, tri-butylamine, three amylamines, three hexyl amines, three heptyl amine, trioctylphosphine amine, diethylamide, triethanolamine, diethanolamine, NaOH, potassium hydroxide, have amino alkoxy silane, ion exchange resin.The addition of catalyzer is 0.01～10 mass parts with respect to monomer 100 mass parts of organosilane etc. preferably.

In addition, consider from the viewpoint of the storage-stable of composition, preferably do not contain catalyzer in the polysiloxane solution after hydrolysis, part condensation, can carry out removing of catalyzer as required.As the method for removing, be not particularly limited, preferably enumerate the processing of water washing and/or ion exchange resin.Water washing refers to utilize evaporator with behind the suitable hydrophobic solvent dilution polysiloxane solution, to wash the concentrated method of organic layer that obtains for several times with water.The processing that has utilized ion exchange resin is the method for instigating polysiloxane solution to contact with suitable ion exchange resin.

Photosensitive siloxane composition of the present invention contains (b) diazonium naphtoquinone compounds.By containing the diazonium naphtoquinone compounds, can form exposure section and be developed the eurymeric that liquid is removed.The diazonium naphtoquinone compounds that uses is not particularly limited, it is the compound that combines diazo naphthoquinone sulfonic acid on the compound with phenol hydroxyl in the mode that forms ester bond, preferably uses the ortho position of phenol hydroxyl of this compound and contraposition to be independently respectively substituent any one the compound shown in hydrogen or the general formula (3).

[changing 4]

(in the formula, R ⁷, R ⁸, R ⁹Represent independently that respectively carbon number is any one of 1～10 alkyl, carboxyl, phenyl, substituted-phenyl.In addition, can be by R ⁷, R ⁸, R ⁹Form ring.）。

In the substituting group shown in the general formula (3), R ⁷, R ⁸, R ⁹Represent independently that respectively carbon number is any one of 1～10 alkyl, carboxyl, phenyl, substituted-phenyl.Alkyl can be without any of substituted compound, substituted compound, can select according to the characteristic of composition.The concrete example of alkyl can be enumerated methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl, n-heptyl, n-octyl, trifluoromethyl, 2-carboxy ethyl.In addition, as the substituting group that replaces at phenyl, can enumerate hydroxyl.In addition, R ⁷, R ⁸, R ⁹Can form ring, concrete example can be enumerated cyclopentane ring, cyclohexane ring, diamantane ring, fluorenes ring.

When being that the ortho position of phenol hydroxyl and contraposition are during as mentioned above respectively independently for substituent any one the compound shown in hydrogen or the general formula (3), even by heat curing, do not produce oxygenolysis yet, therefore do not form the conjugated system compound take the quinonoid compound structure as representative, cured film is not painted, can keep water white transparency.

And, the compound that these diazonium naphtoquinone compounds can be by having the phenol hydroxyl, synthesize with the known esterification of diazo naphthoquinone sulfonic acid chloride.

As the concrete example of the compound with phenol hydroxyl, can enumerate following compound (being Honshu chemical industry (strain) system).

[changing 5]

[changing 6]

In addition, as other preferred form of diazonium naphtoquinone compounds, can be set forth in the compound that combines diazo naphthoquinone sulfonic acid on the compound with phenol hydroxyl shown in the general formula (7) in the mode that forms ester bond.

[changing 7]

(in the formula, R ²⁴, R ²⁵Represent independently that respectively hydrogen, carbon number are that 1～10 alkyl, carbon number are any one of 6～15 aryl.R ²⁶, R ²⁷Represent independently that respectively hydrogen atom, carbon number are any one of 1～8 alkyl, alkoxy, carboxyl, ester group, a plurality of R ²⁶, R ²⁷Can be identical or different.A, b represent 0～4 integer, and c, d represent 1～5 integer.Wherein, a+c and b+d are 1～5 integer, c ≠ d, c+d＞=3.）。

On the compound with phenol hydroxyl shown in the general formula (7), combine the compound of diazo naphthoquinone sulfonic acid as low-molecular-weight and as asymmetrical structure in the mode that forms ester bond, therefore good with the compatibility of (a) polysiloxane, (d) silicate ester compound, even volume is added the diazonium naphtoquinone compounds, do not produce the film gonorrhoea yet.Add the diazonium naphtoquinone compounds by volume, the dissolving contrast of exposure section and unexposed section improves, and the development film that can suppress unexposed section reduces, and realizes that highly sensitive pattern forms.

As the concrete example of the compound with phenol hydroxyl shown in the general formula (7), can enumerate following compound.

[changing 8]

Diazo naphthoquinone sulfonic acid can use 4-diazo naphthoquinone sulfonic acid or 5-diazo naphthoquinone sulfonic acid.4-diazonium naphthoquinone sulphonate compound has absorption in i line (wavelength 365nm) zone, therefore is suitable for the i line exposing.In addition, 5-diazonium naphthoquinone sulphonate compound exists in the wavelength region may of wide region and absorbs, and therefore is suitable for the exposure under the wavelength of wide region.Preferably select 4-diazonium naphthoquinone sulphonate compound, 5-diazonium naphthoquinone sulphonate compound according to the wavelength of exposure.Also 4-diazonium naphthoquinone sulphonate compound and 5-diazonium naphthoquinone sulphonate compound can be used.

The addition of diazonium naphtoquinone compounds is not particularly limited, and is 1～20 mass parts with respect to polysiloxane 100 mass parts preferably, more preferably 2～15 mass parts.The addition of diazonium naphtoquinone compounds is when this preferred scope, and the dissolving contrast of exposure section and unexposed section can be excessively not low yet, has actual photonasty.On the other hand, the compatibility of polysiloxane and diazonium naphtoquinone compounds is held well, the albefaction that does not therefore produce coated film, and what the decomposition of diazonium naphtoquinone compounds caused in the time of can suppressing by heat curing is painted, therefore can keep the water white transparency of cured film.

Photosensitive siloxane composition of the present invention contains (c) solvent.The solvent that uses is not particularly limited, the preferred compound with alcohol hydroxyl group that uses.When using these solvents, polysiloxane and diazonium naphtoquinone compounds dissolve equably, even with the composition coating film forming, also not albefaction of film can realize high transparent.

Above-mentioned compound with alcohol hydroxyl group is not particularly limited, and preferably the boiling point under the atmospheric pressure is 110～250 ℃ compound.Boiling point is when this preferred scope, and the remaining quantity of solvent in the film is few, and the film in the time of can suppressing to solidify shrinks, and can access good flatness.On the other hand, the drying when filming can be not too fast yet, so the film surface is coarse etc., filming property excellence.

As the concrete example of the compound with alcohol hydroxyl group, can enumerate acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxyl-2 pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, propylene glycol list tertbutyl ether, the diglycol monotertiary methyl ether, carbiphene, DPGME, dihydroxypropane single-ethyl ether, 3-methoxyl-n-butyl alcohol, 3-methyl-3-methoxyl-n-butyl alcohol etc.And these compounds with alcohol hydroxyl group can use separately, or will be used in combination more than 2 kinds.

In addition, photosensitive siloxane composition of the present invention only otherwise damage effect of the present invention also can contain other solvent.As other solvent, can enumerate ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether, 3-methoxyl-1-butylacetic acid ester, 3-methyl-3-methoxyl-1-butylacetic acid ester, the ester class of ethyl acetoacetate etc., methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, the ketone of diacetone etc., Anaesthetie Ether, Di Iso Propyl Ether, di-n-butyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the ethers of diglycol ethyl-methyl ether etc., gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, propylene carbonate, 1-METHYLPYRROLIDONE, cyclopentanone, cyclohexanone, cycloheptanone etc.

The addition of solvent is not particularly limited, and is the scope of 100～1000 mass parts with respect to polysiloxane 100 mass parts preferably.

Photosensitive siloxane composition of the present invention contains the silicate ester compound shown in (d) general formula (2).

[changing 9]

(in the formula, R ³～R ⁶Represent independently that respectively hydrogen, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any one of 6～15 aryl.P represents 2～10 integer.）

As the concrete example of the silicate ester compound shown in the general formula (2), can enumerate methyl silicate 51(Japan chemical industry (strain) system), M esters of silicon acis 51, esters of silicon acis 40, esters of silicon acis 45(chemical industry (strain) system of rubbing more), methyl silicate 51, methyl silicate 53A, ethyl silicate 40, silester 48(コルコート (strain) system) etc.

[changing 10]

Wherein, during from heat curing and the reactive angle of polysiloxane consider R preferably ³～R ⁶Be the compound of methyl, specifically, methyl silicate 51(Japan chemical industry (strain) system preferably), M esters of silicon acis 51(chemical industry (strain) system of rubbing more), methyl silicate 51, methyl silicate 53A(コルコート (strain) system).Further; for so the reactivity of raising and polysiloxane; p is preferably 3～5, particularly, methyl silicate 51(Japan chemical industry (strain) system preferably), M esters of silicon acis 51(chemical industry (strain) system of rubbing more), methyl silicate 51(コルコート (strain) system).

Silicate ester compound is high heat-resisting, high transparent compound, and is simultaneously similar with polysiloxane structure, so compatibility is good.Silicate ester compound has a plurality of Si-OR bases in 1 molecule, therefore pass through when heat curing and the reaction of the silanol group in the polysiloxane, and the degree of crosslinking of cured film uprises, and resistance to chemical reagents improves.

The addition of silicate ester compound is not particularly limited, and is 3～20 mass parts with respect to polysiloxane 100 mass parts preferably.3～10 mass parts more preferably.The addition of silicate ester compound is when this preferred scope, and it is large that resistance to chemical reagents improves effect.On the other hand, the development film decrement of unexposed section is few, so the thickness homogeneity is good.

Further, photosensitive polymer combination of the present invention also can contain the metal chelate compound shown in (e) following general formula (6).

[changing 11]

In the metal chelate compound shown in the general formula (6), M is metallic atom.A plurality of R ²¹Can be identical or different, represent respectively hydrogen, alkyl, aryl, thiazolinyl and their substituted compound.A plurality of R ²², R ²³Can be identical or different, represent respectively hydrogen, alkyl, aryl, thiazolinyl, alkoxy and their substituted compound.J is the atomicity of metallic atom M, the integer that k represents more than 0 and j is following.

By containing metal chelate compound, when increasing the development adaptation, can improve the resistance to chemical reagents of the cured film of gained.

In the general formula (6), M is metallic atom, is not particularly limited, but considers from the viewpoint of the transparency, can enumerate the metallic atom of titanium, zirconium, aluminium, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, calcium etc.Wherein, consider from the viewpoint of the resistance to chemical reagents of development adaptation and cured film, preferably zirconium or aluminium.

R ²¹Can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, octadecyl, phenyl, vinyl, allyl, oil base etc.Wherein consider from the angle of stability of compounds, preferably n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-octadecane base, phenyl.R ²²And R ²³Can enumerate hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, phenyl, vinyl, methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-octadecane base, benzyl oxygen base etc.Wherein consider from the angle of easily synthetic and stability of compounds, preferably methyl, the tert-butyl group, phenyl, methoxyl, ethoxy, n-octadecane base.

As the compound shown in the general formula (6); for example as zirconium compounds; can enumerate four n-propoxyzirconium; four n-butoxy zirconiums; four sec-butoxy zirconiums; four phenoxy group zirconiums; tetrem acyl acetone zirconium; four (2; 2; 6; 6-tetramethyl-3, the 5-heptadione) zirconium; tetramethyl acetoacetate zirconium; tetraethyl acetoacetate zirconium; tetramethyl malonic acid zirconium; tetraethyl malonic acid zirconium; four benzoyl acetone zirconiums; four (dibenzoyl methanes) close zirconium (ジ Le コニウ system テトラジベ Application ゾイ Le メタネート); two (oacetic acid) zirconiums (ジ Le コニウ system モノ n-Block トキシアセチ Le アセトネート PVC ス (エチ Le アセトアセテート)) of single n-butoxy diacetone; two (diacetone) zirconiums of single n-butoxy oacetic acid; single n-butoxy tri acetylacetonato zirconium; single n-butoxy tri acetylacetonato zirconium; two (n-butoxies) two (oacetic acid) zirconium; two (n-butoxies) two (diacetone) zirconium; two (n-butoxies) two (ethyl malonic acid) zirconium; two (n-butoxies) two (benzoyl acetone) zirconium; two (n-butoxies) two (dibenzoyl methanes) close zirconium etc.

Aluminium compound can be enumerated aluminium isopropoxide, three positive propoxy aluminium, tri sec-butoxy aluminum, three n-butoxy aluminium, triple phenoxyl aluminium, praseodynium aluminium, three (2,2,6,6-tetramethyl-3, the 5-heptadione) aluminium, aluminium tris(ethylacetoacetate), the pivaloyl aluminium acetate, trimethyl malonic acid aluminium, triethyl malonic acid aluminium, ethyl acetic acid two (isopropoxy) aluminium, diacetone) two (isopropoxy) aluminium, methyl-acetoacetic acid two (isopropoxy) aluminium, octadecyl acetoacetate two (isopropyl alcohol) aluminium, two (oacetic acid) aluminium of single acetyl acetone etc.

As titanium compound, can enumerate four positive propoxy titaniums, four titanium n-butoxide, four sec-butoxy titaniums, four phenoxide titaniums, four titanium acetylacetones, four (2,2,6,6-tetramethyl-3, the 5-heptadione) titanium, tetramethyl acetoacetate titanium, tetraethyl acetoacetate titanium, tetramethyl malonic acid titanium, tetraethyl malonic acid titanium, four benzoyl acetone titaniums, four (dibenzoyl methanes) close titanium, two (oacetic acid) titaniums of single n-butoxy diacetone, two (diacetone) titaniums of single n-butoxy oacetic acid, single n-butoxy tri acetylacetonato titanium, single n-butoxy tri acetylacetonato titanium, two (n-butoxies) two (oacetic acid) titanium, two (n-butoxies) two (diacetone) titanium, two (n-butoxies) two (ethyl malonic acid) titanium, two (n-butoxies) two (benzoyl acetone) titanium, two (n-butoxies) two (dibenzoyl methanes) close titanium, four-2-ethylhexyl titanium dioxide etc.

Wherein, from the dissolubility various solvents, the angle of the stability of compound is considered, four n-propoxyzirconium preferably, four n-butoxy zirconiums, four phenoxy group zirconiums, tetrem acyl acetone zirconium, four (2,2,6,6-tetramethyl-3, the 5-heptadione) zirconium, tetramethyl malonic acid zirconium, tetraethyl malonic acid zirconium, tetraethyl acetoacetate zirconium, two (oacetic acid) zirconiums of two n-butoxies, the zirconium compounds of two (oacetic acid) zirconiums of single n-butoxy diacetone etc., praseodynium aluminium, three (2,2,6,6-tetramethyl-3, the 5-heptadione) aluminium, aluminium tris(ethylacetoacetate), the pivaloyl aluminium acetate, trimethyl malonic acid aluminium, triethyl malonic acid aluminium, ethyl acetic acid two (isopropoxy) aluminium, diacetone) two (isopropoxy) aluminium, methyl-acetoacetic acid two (isopropoxy) aluminium, octadecyl acetoacetate two (isopropyl alcohol) aluminium, the aluminium compound of two (oacetic acid) aluminium of single acetyl acetone etc., four positive propoxy titaniums, four titanium n-butoxide, four phenoxide titaniums, four titanium acetylacetones, four (2,2,6,6-tetramethyl-3, the 5-heptadione) titanium, tetramethyl malonic acid titanium, tetraethyl malonic acid titanium, tetraethyl acetoacetate titanium, two (oacetic acid) titaniums of two n-butoxies, the titanium compound of two (oacetic acid) titaniums of single n-butoxy diacetone etc., the further preferred metal complex system that uses.

The addition of metal chelate compound is not particularly limited, and preferably with respect to polysiloxane 100 weight portions, is 0.1～5 weight portion.0.3～4 weight portion more preferably.By being above-mentioned scope, can take into account with high level the resistance to chemical reagents of development adaptation and cured film.

Further, photosensitive siloxane composition of the present invention also can contain the adjuvant of silane coupling agent, crosslinking chemical, crosslinking accelerator, sensitizer, hot radical propellant, dissolution accelerator, dissolution inhibitor, surfactant, stabilizing agent, defoamer etc. as required.

Photosensitive siloxane composition of the present invention also can contain silane coupling agent.By containing silane coupling agent, with the adaptation raising of substrate.

Concrete example as silane coupling agent, can enumerate methyltrimethoxy silane, methyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, the normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloxy propyl trimethoxy silicane, the 3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propyl group amine, N-phenyl-3-TSL 8330, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, ((3-ethyl-3-oxetanyl) methoxyl) propyl trimethoxy silicane, ((3-ethyl-3-oxetanyl) methoxyl) propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-urea groups propyl-triethoxysilicane, 3-isocyanate group propyl-triethoxysilicane, 3-trimethoxy-silylpropyl succinic acid, the N-tert-butyl group-3-(3-trimethoxy-silylpropyl) succinimide etc.

The addition of silane coupling agent is not particularly limited, and is the scope of 0.1～10 mass parts with respect to polysiloxane 100 mass parts preferably.When addition was this preferred scope, the effect that adaptation improves was abundant, on the other hand, is difficult to carry out condensation reaction between the silane coupling agent in keeping, did not also form the reason of molten residual (the residual り of molten け) when developing.

Photosensitive siloxane composition of the present invention can contain crosslinking chemical.Crosslinking chemical is that to carry out polysiloxane when heat curing crosslinked and take in compound in the resin, by containing the degree of crosslinking of cured film is uprised.The resistance to chemical reagents of cured film improves thus, and the lax (パター Application だれ of pattern can suppress by heat curing the time) reduction of the pattern resolution that causes.

Crosslinking chemical is not particularly limited, and preferably enumerates the compound of group shown in the general formula (4) that has more than 2.

[changing 12]

R ¹⁰Expression hydrogen, carbon number are any one of 1～10 alkyl.And, a plurality of R in the compound ¹⁰Can be identical or different respectively.

In the compound of group shown in the general formula (4) that has more than 2, R ¹⁰Expression hydrogen, carbon number are any one of 1～10 alkyl.And, a plurality of R in the compound ¹⁰Can be identical or different respectively.The concrete example of alkyl can be enumerated methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive decyl.

As the concrete example of the compound of group shown in the general formula (4) that has more than 2, can enumerate following melamine derivative or urea derivative (trade name, three and ケミカ Le (strain) system).

[changing 13]

And above-mentioned crosslinking chemical may be used alone, or two or more kinds may be used in combination.

The addition of crosslinking chemical is not particularly limited, and is the scope of 0.1～10 mass parts with respect to polysiloxane 100 mass parts preferably.The addition of crosslinking chemical when this preferred scope, resin crosslinked fully.On the other hand, can keep the water white transparency of cured film, the storage-stable of composition is excellent.

Photosensitive siloxane composition of the present invention can contain crosslinking accelerator.The crosslinked compound of the polysiloxane when crosslinking accelerator refers to promote heat curing, acidic photoacid generator in the time of can using when heat curing acidic hot acid agent or the decolouring before heat curing exposure.By there being acid in the film when the heat curing, promoted the condensation reaction of unreacted silicon silane alcohol base in the polysiloxane, the degree of crosslinking of cured film uprises.Thus, the resistance to chemical reagents of cured film improves, and the reduction of the lax pattern resolution that causes of pattern can suppress by heat curing the time.

The hot acid agent that uses among the present invention is acidic compound when heat curing, does not preferably produce acid during the preliminary drying after composition coating, or only produces on a small quantity.Therefore be preferably more than the preliminary drying temperature, acidic compound more than 100 ℃ for example.When below the preliminary drying temperature, producing acid, be easy to cause the crosslinked of polysiloxane during preliminary drying, sensitivity, or produce when developing molten residual.

As the concrete example of the hot acid agent of preferred use, can enumerate SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, the above trade name of SI-180L(, three new chemical industry (strain) system), 4-hydroxy phenyl dimethyl sulfonium fluoroform sulphonate, benzyl-4-hydroxy phenyl methyl sulfonium fluoroform sulphonate, 2-methyl-benzyl-4-hydroxy phenyl methyl sulfonium fluoroform sulphonate, 4-acetoxyl group phenyl dimethyl sulfonium fluoroform sulphonate, 4-acetoxyl group phenyl benzyl methyl sulfonium fluoroform sulphonate, 4-methoxycarbonyl oxygen base phenyl dimethyl sulfonium fluoroform sulphonate, benzyl-4-methoxycarbonyl oxygen base phenyl methyl sulfonium fluoroform sulphonate (more than, three new chemical industry (strain) system) etc.And these compounds can use separately, or will be used in combination more than 2 kinds.

The photoacid generator that uses among the present invention is that it is by exposure wavelength 365nm(i line at acidic compound of when exposure decolouring), the 405nm(h line), the 436nm(g line) or these mix the irradiation of light and acidic compound.Therefore, even in the pattern exposure that uses same light source, acidic possibility is arranged also, pattern exposure is compared with the decolouring exposure, and exposure is little, therefore only produces a small amount of acid, can not form problem.In addition, as the acid that produces, the strong acid of perfluoro alkyl sulfonic acid, p-toluenesulfonic acid etc. preferably, the diazonium naphtoquinone compounds that produces carboxylic acid does not have the function of said photoacid generator here, is the material different from crosslinking accelerator of the present invention.

As the concrete example of the photoacid generator of preferred use, can enumerate SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106, the above trade name of PAI-1001(, body どり chemistry (strain) system), SP-077, the above trade name of SP-082(, (strain) ADEKA system), the above trade name of TPS-PFBS(, Japan's compound probability (strain) system), CGI-MDT, the above trade name of CGI-NIT(, チバジャパ Application ((strain)) system), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, the above trade name of WPAG-506(, with light Pure pharmaceutical worker industry (strain) system) etc.And these compounds can use separately, or will be used in combination more than 2 kinds.

In addition, as crosslinking accelerator, also can and be used for above-mentioned hot acid agent and photoacid generator using.The addition of crosslinking accelerator is not particularly limited, and is the scope of 0.01～5 mass parts with respect to polysiloxane 100 mass parts preferably.The addition of crosslinking accelerator is when this preferred scope, and effect is abundant, on the other hand, does not cause the crosslinked of polysiloxane when preliminary drying, during pattern exposure.

Photosensitive siloxane composition of the present invention can contain sensitizer.By containing sensitizer, promoted the reaction as the diazo naphthoquinone compound of emulsion, sensitivity improves, when containing simultaneously photoacid generator as crosslinking accelerator, the reaction when having promoted the decolouring exposure, the resistance to chemical reagents of cured film and pattern resolution improve.

The sensitizer that uses among the present invention is not particularly limited, the preferred use by the sensitizer thermal treatment gasification and/or that fade by irradiation.This sensitizer need to be for the 365nm(i line as the wavelength of light source in pattern exposure, the decolouring exposure), the 405nm(h line), the 436nm(g line) have an absorption, but when directly remaining in the cured film, there are absorption so water white transparency reduction in the visible region.Therefore for the reduction of the water white transparency that prevents from being caused by sensitizer, used sensitizer is the compound (sensitizer) of the thermal treatment gasification by heat curing etc. and/or the compound (sensitizer) that the irradiation by decolouring exposure etc. fades preferably.

As what gasify by above-mentioned thermal treatment, and/or the concrete example of the sensitizer that fades by irradiation, can enumerate 3, the cumarin of 3 '-carbonyl two (diethyl amino coumarin) etc., 9, the anthraquinone of 10-anthraquinone etc., benzophenone, 4,4 '-dimethoxy-benzophenone, acetophenone, the 4-methoxyacetophenone, the aromatic ketone of benzaldehyde etc., biphenyl, 1, the 4-dimethylnaphthalene, 9-Fluorenone, fluorenes, luxuriant and rich with fragrance, benzophenanthrene, pyrene, anthracene, the 9-phenylanthracene, 9-methoxyl anthracene, 9, the 10-diphenylanthrancene, 9, two (4-methoxyphenyl) anthracenes of 10-, 9, two (triphenyl silicyl) anthracenes of 10-, 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxy anthracene, 9,10-dibutoxy anthracene, 9,10-two amoxy anthracenes, the 2-tert-butyl group-9,10-dibutoxy anthracene, two (trimethyl silyl ethinyl) anthracenes of 9,10-etc. condense aromatic series etc.

In these sensitizers, the sensitizer that gasifies by thermal treatment preferably causes the pyrolysate distillation that is formed by distillation, evaporation, thermal decomposition or the sensitizer that evaporates by thermal treatment.In addition, as the gasification temperature of sensitizer, preferably 130 ℃～400 ℃, further preferably 150 ℃～250 ℃.The gasification temperature of sensitizer is when this preferred scope, and sensitizer is difficult to gasification in preliminary drying, therefore can exist in step of exposure, can keep high sensitivity.On the other hand, sensitizer gasifies when heat curing, does not therefore remain in the cured film, can keep water white transparency.In addition, in order fully to gasify when the heat curing, the gasification temperature of sensitizer is preferably below 250 ℃.

On the other hand, the sensitizer that fades by irradiation considers from the angle of the transparency, preferably the sensitizer that fades by irradiation of the absorption of visible region.In addition, the compound that further preferably fades by irradiation is the compound that carries out dimerization by irradiation.Carry out dimerization by irradiation, molecular weight increases and insoluble thus, thus the effect that can obtain that resistance to chemical reagents improves, thermotolerance improves, reduce from the extract of transparent cured film.

In addition, sensitizer is from realizing highly sensitive aspect, carrying out the aspect consideration that dimerization fades, preferably anthracene based compound by irradiation, further, since 9,10 be that the anthracene based compound of hydrogen is to thermally labile, therefore preferably 9,10-two replaces the anthracene based compounds.Further, consider from reactive angle of the deliquescent raising of sensitizer and photodimerization reaction, be preferably 9 shown in the general formula (5), 10-dialkoxy anthracene based compound.

[changing 14]

The R of general formula (5) ¹¹～R ¹⁸Represent independently that respectively hydrogen, carbon number are the organic group that 1～20 alkyl, alkoxy, thiazolinyl, aryl, acyl group and they have been substituted.The concrete example of alkyl can be enumerated methyl, ethyl, n-pro-pyl.The concrete example of alkoxy can be enumerated methoxyl, ethoxy, propoxyl group, butoxy, amoxy.The concrete example of thiazolinyl can be enumerated vinyl, acryloxy propyl group, methacryloxypropyl.The concrete example of aryl can be enumerated phenyl, tolyl, naphthyl.The concrete example of acyl group can be enumerated acetyl group.Consider R from the gasification of compound, reactive angle of photodimerization ¹¹～R ¹⁸Preferably hydrogen or carbon number are the organic group till 1～6.Further preferred R ¹¹, R ¹⁴, R ¹⁵, R ¹⁸Be hydrogen.

The R of general formula (5) ¹⁹, R ²⁰The expression carbon number is the organic group that 1～20 alkoxy and they have been substituted.The concrete example of alkoxy can be enumerated methoxyl, ethoxy, propoxyl group, butoxy, amoxy, but the angle of the bleaching reaction that causes from the dissolubility of compound with by photodimerization considers, preferably propoxyl group, butoxy.

The addition of sensitizer is not particularly limited, and preferably with respect to polysiloxane 100 mass parts, adds with the scope of 0.01～5 mass parts.The addition of sensitizer is when this preferred scope, and the transparency does not reduce, and sensitivity does not descend yet.

Formation method for the cured film of having used photosensitive siloxane composition of the present invention describes.By known methods such as spinner, slits composition of the present invention is coated on the bottom substrate, utilizes the heating arrangement of heating plate, baking oven etc. to carry out preliminary drying.Preliminary drying carried out under 50～150 ℃ scope 30 seconds～30 minutes, and pre-baked thickness is preferably 0.1～15 μ m.

Use stepper (ステッパー), mirror projection print plate litho machine (MPA), directional light mask aligner (パラレ Le ライトマス Network アライナー) ultraviolet-visible exposure machine (PLA) etc. behind the preliminary drying, via required mask with 10～4000J/m ²About (conversion of wavelength 365nm exposure) carry out pattern exposure.

By the dissolving exposure section of developing, can obtain the pattern of eurymeric after the exposure.As developing method, preferably utilize the method for spray, dipping, blade etc. in developer solution, to flood 5 seconds～10 minutes.As developer solution, can use known alkaline developer.As concrete example, can enumerate the aqueous solution of the quaternary ammonium salts such as amine, Tetramethylammonium hydroxide, choline such as inorganic bases such as containing one kind or two or more alkali-metal oxyhydroxide, carbonate, phosphate, silicate, borate, 2-DEAE diethylaminoethanol, monoethanolamine, diethanolamine etc.In addition, preferred water flushing after developing, if necessary, the heating arrangement that also can utilize heating plate, baking oven etc. dehydrates baking 50～150 ℃ scope.

Then, the exposure of preferably decolouring.By the exposure of decolouring, the unreacted diazonium naphtoquinone compounds that remains in the film produces the light decomposition, and the optical transparency of film further improves.As the method for decolouring exposure, the ultraviolet-visible exposure machine of use PLA etc. is with 100～20000J/m ²About (conversion of wavelength 365nm exposure) to whole exposure.

If necessary; the film that decolouring has been exposed with the heating arrangement of heating plate, baking oven etc. after 50～150 ℃ scope is carried out soft baking in 30 seconds～30 minutes; the heating arrangement that utilizes heating plate, baking oven etc. carries out curing about 1 hour 150～450 ℃ scope, can form thus TFT in the display element with the interlayer dielectric in the diaphragm of planarization film, touch-screen, dielectric film, the semiconductor element or the core in the optical waveguide, the such cured film of cladding material.

Using the light transmission of the per 3 μ m thickness of cured film under wavelength 400nm of photosensitive siloxane composition making of the present invention is more than 90%, more preferably more than 92%.The light transmission of cured film when this preferred scope, in the situation about using with planarization film as the TFT substrate of liquid crystal display cells, backlight by the time do not produce look and change, white displays can be with little yellow yet.

The transmissivity of above-mentioned per 3 μ m thickness under wavelength 400nm utilizes following method to try to achieve.Use spinner that composition is spin-coated on the TEMPAX glass plate with rotation number arbitrarily, use heating plate at 100 ℃ of preliminary dryings that carry out 2 minutes.Then, as decolouring exposure, use PLA to whole of film with extra-high-pressure mercury vapour lamp with 3000J/m ²(conversion of wavelength 365nm exposure) exposure, the use baking oven 220 ℃ of heat curings of carrying out 1 hour, is made the cured film of thickness 3 μ m in air.Use (strain) Shimadzu Seisakusho Ltd. system " MultiSpec "-1500 to measure the UV, visible light optical absorption spectra of the cured film of gained, try to achieve the transmissivity under the wavelength 400nm.

This cured film can be suitable for the TFT substrate of liquid crystal display cells etc. with in the core of the interlayer dielectric of the diaphragm of planarization film, touch-screen, dielectric film, semiconductor element or optical waveguide, the cladding material etc.

Element of the present invention refers to have liquid crystal display cells or organic EL display element, touch-screen, semiconductor element or the optical waveguide material of above-mentioned such cured film, especially, can be used as the TFT substrate is used for having this film effectively with planarization film liquid crystal display cells, and the touch-screen that effectively is used for having this film as dielectric film.

Embodiment

Below enumerate embodiment, and then specifically describe the present invention, but the present invention is not subjected to the restriction of these embodiment.And, in the compound that uses, for the compound that uses the letter language, as shown below.

DAA: diacetone alcohol

PGMEA: propylene glycol monomethyl ether

PGME: propylene glycol monomethyl ether

In addition, the weight-average molecular weight (Mw) of the solid constituent concentration of polysiloxane solution, acrylic resin soln and polysiloxane, acryl resin is obtained as following.

(1) solid constituent concentration

In the aluminium cup, take by weighing polysiloxane (acryl resin) solution 1g, use heating plate 250 ℃ of heating 30 minutes, liquid is partly evaporated.Residual solid composition in the aluminium cup of weighing after heating is tried to achieve the solid constituent concentration of polysiloxane (acryl resin) solution.

(2) weight-average molecular weight

Weight-average molecular weight is utilized GPC(Waters society system 996 type デテクター, developing solvent: tetrahydrofuran) and by polystyrene conversion try to achieve.

［ synthesis example 1: polysiloxane solution (a) synthetic ］

The methyltrimethoxy silane of in the three-neck flask of 500ml, packing into 54.48g(0.4mol), phenyltrimethoxysila,e 99.15g(0.5mol), 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane 24.64g(0.1mol), diacetone alcohol (being designated hereinafter simply as DAA) 163.35g, be added on that dissolving phosphoric acid 0.535g(is 0.3 quality % with respect to adding monomer among the water 54g in 10 minutes while at room temperature stir to use) phosphate aqueous solution that forms.Then, flask is immersed in 40 ℃ the oil bath, stirs after 30 minutes, with 30 minutes oil bath is warming up to 115 ℃.Heat up beginning after 1 hour, and the interior temperature of solution reaches 100 ℃, adds afterwards thermal agitation 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (a).And, add in the thermal agitation, with the 0.05l(liter)/min flows into nitrogen.In reaction, distillate methyl alcohol, hydration meter 120g as accessory substance.

The solid constituent concentration of the polysiloxane solution of gained (a) is 40 quality %, and the weight-average molecular weight of polysiloxane is 6500.And the phenyl containing ratio in the polysiloxane is 50 % by mole with respect to the Si atom.

［ synthesis example 2: polysiloxane solution (b) synthetic ］

In the three-neck flask of 500ml, add methyltrimethoxy silane 40.86g(0.3mol), phenyltrimethoxysila,e 99.15g(0.5mol), 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane 12.32g(0.05mol), rub chemical industry (strain) system of M esters of silicon acis 51() 17.63g(counts 0.15mol with the silane atom molal quantity more), propylene glycol monomethyl ether (being designated hereinafter simply as PGMEA) 153.66g was added on that to have dissolved phosphoric acid 0.51g(among the water 53.55g be 0.3 quality % with respect to adding monomer in 10 minutes while at room temperature stir to use) phosphate aqueous solution that forms.Then, in the oil bath with 40 ℃ of flask immersions, stir after 30 minutes, with 30 minutes oil bath is warming up to 115 ℃.After beginning to heat up 1 hour, the interior temperature of solution arrives 100 ℃, adds afterwards thermal agitation 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (b).And, add in the thermal agitation, with the 0.05l(liter)/min flows into nitrogen.Distillate methyl alcohol, hydration meter 120g as accessory substance in the reaction.

The solid constituent concentration of the polysiloxane solution of gained (b) is 40 quality %, and the weight-average molecular weight of polysiloxane is 10000.And the phenyl containing ratio in the polysiloxane is 50 % by mole with respect to the Si atom.

［ synthesis example 3: polysiloxane solution (c) synthetic ］

Adding methyltrimethoxy silane 88.53g(0.65mol in the three-neck flask of 500ml), phenyltrimethoxysila,e 49.58g(0.25mol), 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane 24.64g(0.1mol), DAA 144.83g, be added on that to have dissolved phosphoric acid 0.081g(among the water 54g be 0.05 quality % with respect to adding monomer in 10 minutes while at room temperature stir to use) phosphate aqueous solution.Then, flask is immersed in 40 ℃ the oil bath, stirs after 30 minutes, with 30 minutes oil bath is warming up to 115 ℃.The interior temperature that begins solution after 1 hour that heats up reaches 100 ℃, adds afterwards thermal agitation 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (c).And, add in the thermal agitation with the 0.05l(liter)/min flows into nitrogen.Distillate methyl alcohol, hydration meter 120g as accessory substance in the reaction.

The solid constituent concentration of the polysiloxane solution of gained (c) is 40 quality %, and the weight-average molecular weight of polysiloxane is 9000.And the phenyl containing ratio in the polysiloxane is 25 % by mole with respect to the Si atom.

［ synthesis example 4: polysiloxane solution (d) synthetic ］

Adding methyltrimethoxy silane 20.43g(0.15mol in the three-neck flask of 500ml), phenyltrimethoxysila,e 158.64g(0.8mol), 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane 12.32g(0.05mol), DAA179.54g, to have dissolved phosphoric acid 0.383g(among the water 54g be 0.2 quality % with respect to the adding monomer with being added in 10 minutes Yi Bian at room temperature stir on one side) phosphate aqueous solution that forms.Then, flask is immersed in 40 ℃ the oil bath, stirs after 30 minutes, with 30 minutes oil bath is warming up to 115 ℃.Heat up beginning after 1 hour, and the interior temperature of solution reaches 100 ℃, adds afterwards thermal agitation 3 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (d).And, in adding thermal agitation, with the 0.05l(liter)/the mobile nitrogen of min.In reaction, distillate methyl alcohol, hydration meter 120g as accessory substance.

The solid constituent concentration of the polysiloxane solution of gained (d) is 40 quality %, and the weight-average molecular weight of polysiloxane is 7000.And the phenyl containing ratio in the polysiloxane is 80 % by mole with respect to the Si atom.

［ synthesis example 5: acrylic resin soln (a) synthetic ］

In the flask of 500ml, add 2,2 '-azoisobutyronitrile 5g, PGMEA 150g.Then, add methacrylic acid 27g, methacrylic acid benzyl ester 38g, three ring ［ 5.2.1.02,6 ］ decane-8-ylmethyl acrylate 35g, at room temperature stir a moment, after carrying out the nitrogen displacement in the flask, added thermal agitation 5 hours at 70 ℃.Then, in the solution of gained, add methyl propenoic acid glycidyl base ester 15g, dimethyl benzyl amine 1g, p methoxy phenol 0.2g, added thermal agitation 4 hours at 90 ℃, obtain acrylic resin soln (a).

The solid constituent concentration of the acrylic resin soln of gained (a) is 43 quality %, and the weight-average molecular weight of acryl resin is 31400.

［ synthesis example 6: diazonium naphtoquinone compounds (a) synthetic ］

Drying nitrogen flows down, and makes TrisP-PA(trade name, Honshu chemical industry (strain) system) 21.23g(0.05mol) and 5-diazo naphthoquinone sulfonic acid chloride 37.62g(0.14mol) be dissolved among the Isosorbide-5-Nitrae-diox 450g, making its temperature is room temperature.To wherein dripping the triethylamine 15.58g(0.154mol that has mixed with Isosorbide-5-Nitrae-diox 50g), making in the system is not more than 35 ℃.Stirred 2 hours at 30 ℃ after dripping.Triethyl amine salt is filtered, filtrate is added to the water.Then, collect the precipitation of separating out by filtering.Should precipitate with the vacuum drier drying, obtain the diazonium naphtoquinone compounds (a) of following structure.

[changing 15]

。

［ synthesis example 7: diazonium naphtoquinone compounds (b) synthetic ］

Drying nitrogen flows down, and makes TrisP-HAP(trade name, Honshu chemical industry (strain) system) 15.32g(0.05mol) and 5-diazo naphthoquinone sulfonic acid chloride 26.87g(0.1mol) be dissolved among the Isosorbide-5-Nitrae-diox 450g, making its temperature is room temperature.To wherein dripping the triethylamine 11.13g(0.11mol that has mixed with Isosorbide-5-Nitrae-diox 50g), making in the system is not more than 35 ℃.Stirred 2 hours at 30 ℃ after dripping.Triethyl amine salt is filtered, filtrate is added to the water.Then, collect the precipitation of separating out by filtering.Should precipitate with the vacuum drier drying, obtain the diazonium naphtoquinone compounds (b) of following structure.

[changing 16]

。

［ synthesis example 8: diazonium naphtoquinone compounds (c) synthetic ］

Drying nitrogen flows down, and makes Ph-cc-AP-MF(trade name, Honshu chemical industry (strain) system) 15.32g(0.05mol) and 5-diazo naphthoquinone sulfonic acid chloride 37.62g(0.14mol) be dissolved among the Isosorbide-5-Nitrae-diox 450g, making its temperature is room temperature.To wherein dripping the triethylamine 15.58g(0.154mol that has mixed with Isosorbide-5-Nitrae-diox 50g), making in the system is not more than 35 ℃.Stirred 2 hours at 30 ℃ after dripping.Triethyl amine salt is filtered, filtrate is added to the water.Then, collect the precipitation of separating out by filtering.Should precipitate with the vacuum drier drying, obtain the diazonium naphtoquinone compounds (c) of following structure.

[changing 17]

。

(embodiment 1)

Polysiloxane solution (a) 25.51g with gained in the synthesis example 1, diazonium naphtoquinone compounds (c) 0.92g of gained in the synthesis example 8, M esters of silicon acis 51(trade name as silicate ester compound, the chemical industry (strain) that rubs system) 1.02g more, KBM303(2-(3 as silane coupling agent, the 4-epoxycyclohexyl) ethyl trimethoxy silane, trade name, SHIN-ETSU HANTOTAI's chemical industry (strain) system) 0.20g, CGI-MDT(trade name as crosslinking accelerator, チバジャパ Application (strain) system) 0.10g, DPA(9 as sensitizer, 10-dipropoxy anthracene, trade name, Kawasaki changes into industry (strain) system) 0.05g, DAA3.44g as solvent, PGMEA18.75g mixes under amber light, stir, after forming uniform solution, utilize the filtrator of 0.2 μ m to filter, make composition 1.Form and be shown in table 1.And, be the compound of structure shown in following as the M esters of silicon acis 51 of silicate ester compound, as the CGI-MDT of crosslinking accelerator.

[changing 18]

Use spinner (ミカサ (strain) 1H-360S processed) with after rotation number is spin-coated on composition 1 on silicon chip and the OA-10 glass plate (NEG (strain) system) arbitrarily, use heating plate (large Japanese スクリー Application is made (strain) SCW-636 processed) at 100 ℃ of preliminary dryings 2 minutes, the film of making thickness 3 μ m.After the gray scale mask that uses directional light mask aligner (being designated hereinafter simply as PLA) (キヤノ Application (strain) PLA-501F processed) that the film of making is used by sensitivity determination with extra-high-pressure mercury vapour lamp carries out pattern exposure, use automatic developing device (Takizawa swamp industry (strain) AD-2000 processed), be used as ELM-D(trade name, the ガス of Mitsubishi chemistry (strain) system of 2.38 quality % tetramethylammonium hydroxide aqueous solutions) carry out the spray development in 80 seconds, then water carries out the flushing in 30 seconds.Then, as decolouring exposure, use PLA(キヤノ Application (strain) PLA-501F processed), to whole of film with extra-high-pressure mercury vapour lamp with the conversion of 3000J/m2(wavelength 365nm exposure) expose.Then, use heating plate 110 ℃ of soft bakings of carrying out 2 minutes, then use baking oven (タバイエスペッ Network (strain) IHPS-222 processed) in air, to solidify 1 hour at 220 ℃, make cured film.

The evaluation result of sensitometric characteristic and cured film characteristic is shown in table 2.And the evaluation in the table is carried out with following methods.And the evaluation of following (3)～(6) uses the silicon chip substrate to carry out, and the evaluation of (8), (9) uses the OA-10 glass plate to carry out.

(3) determining film thickness

Use " ラ system ダエース " STM-602(trade name, large Japanese スクリー Application system) measure with 1.50 refractive index.

(4) residual film ratio calculates

Residual film ratio is calculated according to following formula.

Unexposed the pre-baked thickness of thickness ÷ * 100 after residual film ratio (%)=development.

(5) sensitivity calculates

Exposure, develop after, will make the live width of 10 μ m and interval (ライ Application ア Application De スペース) pattern form the exposure (below be referred to as the suitableeest exposure) of 1 to 1 width as sensitivity.

(6) resolution calculates

With the minimum pattern size after the development of the suitableeest exposure as resolution after developing, with the minimum pattern size after solidifying as resolution after solidifying.

(7) mensuration of rate of mass reduction

With composition approximately 100mg put into the aluminium box, use thermal mass determinator (TGA-50, (strain) Shimadzu Seisakusho Ltd. system) in the nitrogen atmosphere, the programming rate measured with 10 ℃/minute is heated to 300 ℃, keep making under this state it to be heating and curing 1 hour, the rate of mass reduction when then being warming up to 400 ℃ with 10 ℃/minute programming rate.Quality when measure arriving 300 ℃ is further measured the quality when arriving 400 ℃, and the quality when trying to achieve with 300 ℃ poor obtained the mass fraction that reduces as rate of mass reduction.

(8) mensuration of light transmission

Use " MultiSpec "-1500(trade name, (strain) Shimadzu Seisakusho Ltd.), at first only measure the OA-10 glass plate, with this UV, visible light optical absorption spectra as reference.Then form the cured film (not carrying out pattern exposure) of composition at the OA-10 glass plate, this sample measured with single beam, try to achieve the light transmission under the wavelength 400nm of per 3 μ m, will with the difference of the reference light transmission as cured film.

(9) evaluation of resistance to chemical reagents

Form the cured film (not carrying out pattern exposure) of composition at the OA-10 glass plate, make 10 * 10 square formation (マス order) in this cured film with the 1mm interval of cutting knife.Then, at ITO etching solution (hydrochloric acid/potassium chloride/water=6/8/84(mass ratio)) in the dipping 50 ℃ * 300 seconds.Then, attach hinge in square formation, the rate of peeling off of the cured film on the square formation when peeling off is evaluated as 0%:A, below 5%: B, 5～35%:C, more than 35%: F.

(embodiment 2～13, comparative example 1～4)

Composition 2～17 as the composition of record in the table 1, is similarly made with composition 1.And, methyl silicate 53A, ethyl silicate 40, silester 48(trade name, コ Le コート (strain) system used as silicate ester compound), KBM403(trade name, SHIN-ETSU HANTOTAI's chemical industry (strain) system used as silane coupling agent), the NIKALAC MX-270 that uses as crosslinking chemical, NIKALAC MW-30HM(trade name, three and ケミカ Le (strain) system) be the compound of structure shown in following.

[table 1]

[changing 19]

Use each composition of gained, carry out similarly to Example 1 the evaluation of each composition.Wherein, in the evaluation of comparative example 2, development is that the spray that utilizes 0.4 quality % tetramethylammonium hydroxide aqueous solution (with the ELM-D dilute with water solution) to carry out for 80 seconds develops.The results are shown in table 2.Comparative example 1,2 and 4 does not contain the silicate ester compound shown in the general formula (2), so the resistance to chemical reagents in the cured film characteristic is poor.In addition, for comparative example 3, because resin is acryl resin, so the light transmission in the cured film characteristic is poor.

[table 2]

The industry utilizability

The present invention can be suitable for photosensitive siloxane composition, and thin film transistor (TFT) (TFT) substrate that this photosensitive siloxane composition is used to form liquid crystal display cells, organic EL display element etc. is with the core of the interlayer dielectric of the diaphragm of planarization film, touch-screen, dielectric film, semiconductor element or optical waveguide, cladding material etc.

Claims

1. photosensitive siloxane composition, it contains

(a) reaction synthesize more than a kind the polysiloxane, (b) diazonium naphtoquinone compounds, (c) solvent by making the organosilane shown in the general formula (1) and (d) silicate ester compound shown in the general formula (2),

[changing 1]

In the following formula (1), R ¹Expression hydrogen, carbon number are that 1～10 alkyl, carbon number are that 2～10 thiazolinyl, carbon number are any one of 6～15 aryl, a plurality of R ¹Can be identical or different respectively, R ²Expression hydrogen, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any one of 6～15 aryl, a plurality of R ²Can be identical or different respectively, n represents 0～3 integer;

[changing 2]

In the following formula (2), R ³～R ⁶Represent independently that respectively hydrogen, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any one of 6～15 aryl, p represents 2～10 integer.

2. photosensitive siloxane composition according to claim 1, wherein, in the silicate ester compound shown in (d) general formula (2), R ³～R ⁶Be methyl.

3. photosensitive siloxane composition according to claim 1 wherein, further contains the metallo-chelate shown in (e) general formula (6),

[changing 3]

In the formula, M is metallic atom, a plurality of R ²¹Can be identical or different, represent respectively hydrogen, alkyl, aryl, thiazolinyl and their substituted compound, R ²², R ²³Can be identical or different, represent respectively hydrogen, alkyl, aryl, thiazolinyl, alkoxy and their substituted compound, j represents the atomicity of metallic atom M, the integer that k represents more than 0 and j is following.

4. photosensitive siloxane composition according to claim 1, wherein, (b) the diazonium naphtoquinone compounds is the compound that combines diazo naphthoquinone sulfonic acid on the compound with phenol hydroxyl shown in the general formula (7) in the mode that forms ester bond,

[changing 4]

In the following formula (7), R ²⁴, R ²⁵Represent independently that respectively hydrogen, carbon number are that 1～10 alkyl, carbon number are any one of 6～15 aryl, R ²⁶, R ²⁷Represent independently that respectively hydrogen atom, carbon number are any one of 1～8 alkyl, alkoxy, carboxyl, ester group, a plurality of R ²⁶, R ²⁷Can be identical or different, a, b represent 0～4 integer, and c, d represent 1～5 integer, and wherein a+c and b+d are 1～5 integer, c ≠ d, c+d＞=3.

5. cured film, it is the cured film that is formed by photosensitive siloxane composition claimed in claim 1, wherein, the light transmission of the per 3 μ m thickness under the wavelength 400nm is more than 90%.

6. element, it possesses cured film claimed in claim 5.